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I would say that, as stated, that question is way too general and vague to be answered in a single forum post (probably not even in a dozen posts).

Much of it will depend on what you mean by "web site" in this specific instance; and the fact that you use PHP as your server-side programming language has very little to do with the process -- and determining up front that PHP is the right answer is probably putting the proverbial cart before the horse anyway.

"Please give us a simple answer, so that we don't have to think, because if we think, we might find answers that don't fit the way we want the world to be."
~ Terry Pratchett in Nation

I agree with NogDog's comments. If you are not already familiar with developing in HTML/CSS then you are starting at the wrong point.

However, assuming that you are already familiar with developing in HTML/CSS, the first thing you need to do if you want to develop in PHP is to set up a local host. This is because PHP, being a server language, only runs on servers not browsers. Fortunately, these can be downloaded for free, and, in my opinion. the best one for a Windows platform is Wamp Server. It is easy and safe to set up on a single workstation, which is how it is configured by default. Setting one up to work across a LAN takes some care as you can easily leave your whole network open to malicious attacks. I can give you advice on that if you need it...